The thermal decomposition of the chloride adduct of pentaerythritol tetranitrate (PETN) has been studied with a new cross-flow sample introduction, dual shutter, ion mobility spectrometer. Chloride anions, produced in an ion source, react with PETN introduced by a nebulizer into a flow of heated gas orthogonal to the drift gas flow. This cross-flow procedure allows PETN introduction from solution at drift gas temperatures where the PETN∙Cl¯ intensity is sufficiently intense and stable to allow characterization of its thermal decomposition kinetics. Dual shutter operation allows the selection of PETN∙Cl¯ for observation of its thermal decomposition in the electrostatic drift field. In this adduct, Cl¯ displaces NO₃¯ in an S_N2 reaction with an activation energy of 80 ± 7 kJ mol^-1 over the temperature range 145 °C–165 °C. At temperatures above 165 °C, decomposition occurs before ion selection, resulting in the release of NO₃¯ and PETN∙NO₃¯ becomes the sole adduct ion. PETN∙NO₃¯ decomposes over the temperature range 175 °C–200 °C with an activation energy of 92 ± 8 kJ mol^-1. Density functional calculations are used to interpret the results.

季戊四醇四硝酸酯 (PETN) 的氯化物加合物的热分解已使用新型错流进样、双快门、离子迁移谱仪进行了研究。离子源中产生的氯离子与雾化器引入的 PETN 反应，进入与漂移气流正交的加热气流中。这种错流程序允许在漂移气体温度下从溶液中引入 PETN，其中 PETN∙Cl¯ 强度足够强和稳定，可以表征其热分解动力学。双快门操作允许选择 PETN∙Cl¯ 来观察其在静电漂移场中的热分解。在此加合物，CL置换NO ₃以S＆OverBar; _Ñ 2反应，用80±7千焦mol的活化能^-1在 145 °C–165 °C 的温度范围内。在高于 165 °C 的温度下，分解发生在离子选择之前，导致释放 NO ₃ ¯ 和 PETN∙NO ₃ ¯ 成为唯一的加合物。PETN∙NO ₃ ¯ 在 175 °C–200 °C 的温度范围内分解，活化能为 92 ± 8 kJ mol ^-1。密度泛函计算用于解释结果。